CN113717309B - Processing modified additive and preparation method thereof - Google Patents
Processing modified additive and preparation method thereof Download PDFInfo
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- CN113717309B CN113717309B CN202110947357.0A CN202110947357A CN113717309B CN 113717309 B CN113717309 B CN 113717309B CN 202110947357 A CN202110947357 A CN 202110947357A CN 113717309 B CN113717309 B CN 113717309B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L27/24—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a processing modification auxiliary agent and a preparation method thereof. An acrylic ester processing aid ACR and an impact modifier MBS are added into a CPVC resin formula system, and the processing aid ACR and the impact modifier MBS can cause higher torque of CPVC in the processing process and also can cause the reduction of the Vicat softening point of the CPVC fire-fighting pipe in the using process. Based on the problems, the invention provides a processing modification auxiliary agent, the processing modification auxiliary agent is obtained by copolymerization of vinyl chloride, vinylidene chloride and vinyl versatate serving as raw materials, and a vinyl chloride chain structure and a vinylidene chloride chain structure in a molecular structure of the processing modification auxiliary agent have good compatibility with CPVC, so that the processing modification auxiliary agent is very beneficial to improving the comprehensive performance of the CPVC fire fighting pipe.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a processing modification additive and a preparation method thereof.
Background
In recent years, plastic pipes have been developed unprecedentedly, in favor of the explosive development of real estate and the need for old community transformation. Among them, CPVC fire hose is favored by people because of its characteristics of flame retardance, heat resistance, chemical corrosion resistance, bacteriostasis, and long life, and its usage amount is getting larger and larger.
The CPVC fire-fighting pipe has high requirements on the processing performance, the heat resistance, the flame retardant performance and the impact resistance. In order to improve the processability of the CPVC fire-fighting pipe, an acrylate processing aid ACR and an impact modifier MBS are added into a CPVC resin formula system, wherein the impact modifier MBS and the processing aid ACR can cause higher torque of the CPVC in the processing process in the use process, and can also cause the reduction of the Vicat softening point and the reduction of the flame retardant property of the CPVC fire-fighting pipe.
Facing the continuously growing CPVC industry, the method has extremely strong commercial significance for obtaining a processing-aid modifier with good processing performance, high Vicat softening point and excellent flame retardant property
Disclosure of Invention
Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: the addition of the acrylate processing aid ACR to the CPVC resin formulation system results in higher torque of the CPVC during processing and also results in a decrease in the Vicat softening point of the CPVC fire hose.
The technical scheme adopted by the invention for solving the technical problem is as follows: the invention provides a processing modification additive which comprises the following components in parts by weight:
the sum of the parts by weight of the chloroethylene, the vinylidene chloride and the vinyl versatate is 70 parts.
Specifically, the initiator is a mixture of azobisisobutyronitrile and tert-butyl peroxypivalate in a weight ratio of 3.
Specifically, the dispersing agent is a mixture consisting of polyvinyl alcohol KH-20, hydroxypropyl methyl cellulose E50 and polyvinyl alcohol LL-02 in a weight ratio of 3.
Specifically, the processing modified additive is characterized by being prepared according to the following steps in parts by weight:
(1) Adding vinyl versatate, initiator, 3/4 deionized water and 3/4 dispersant into a reaction kettle in sequence according to the formula amount, vacuumizing, adding 1/2-3/5 vinyl chloride into the reaction kettle when the vacuum degree reaches 0.09MPa, and stirring for 1-1.5h to uniformly disperse the materials;
(2) Adding the rest deionized water, the dispersing agent, vinyl chloride and vinylidene chloride into a stirring dispersion kettle, and stirring for 1-2 hours to obtain a fully dispersed monomer dispersion liquid;
(3) Heating the reaction kettle in the step (1) to 58-68 ℃, starting a reaction in the reaction kettle, continuously and uniformly adding the monomer dispersion liquid prepared in the step (2) within 2-3h when the pressure in the reaction kettle is reduced by 0.25MPa, and stripping the reaction kettle to recover unreacted chloroethylene in the system when the pressure in the reaction kettle is reduced to be below 0.3 MPa;
(4) And (3) pouring out the materials in the reaction kettle, sequentially performing dehydration, rinsing, centrifugation and drying treatment, and then screening the dried materials by using a 40-mesh screen to obtain the material.
The invention has the beneficial effects that:
(1) The self-made processing-assistant modifier is obtained by copolymerizing vinyl chloride, vinylidene chloride and vinyl versatate serving as raw materials, and a vinyl chloride chain structure and a vinylidene chloride chain structure in a molecular structure of the processing-assistant modifier have good compatibility with CPVC, so that the self-made processing-assistant modifier is very favorable for improving the comprehensive performance of the CPVC fire fighting pipe;
(2) The processing-assistant modifier disclosed by the invention contains vinylidene chloride and vinyl versatate structures with low glass transition temperature in a molecular structure, has a good plasticizing effect in CPVC, and can effectively improve the processing performance of a CPVC fire-fighting pipe and reduce the processing load.
Detailed Description
The present invention will now be described in further detail with reference to examples.
The initiator used in the following examples of the present invention was a mixture of azobisisobutyronitrile and tert-butyl peroxypivalate in a weight ratio of 3.
The dispersing agent used in the following examples is a mixture consisting of polyvinyl alcohol KH-20, hydroxypropyl methylcellulose E50 and polyvinyl alcohol LL-02 in a weight ratio of 3.
The processing modification additive in the following embodiment of the invention is prepared according to the following steps in parts by weight:
(1) Adding vinyl versatate, initiator, 3/4 deionized water and 3/4 dispersant into a reaction kettle in sequence according to the formula amount, vacuumizing, adding 1/2-3/5 vinyl chloride into the reaction kettle when the vacuum degree reaches 0.09MPa, and stirring for 1-1.5 hours to uniformly disperse the materials;
(2) Adding the rest deionized water, the dispersant, vinyl chloride and vinylidene chloride into a stirring dispersion kettle, and stirring for 1-2h to obtain a fully dispersed monomer dispersion liquid;
(3) Heating the reaction kettle in the step (1) to 58-68 ℃, starting to react in the reaction kettle, continuously and uniformly adding the monomer dispersion liquid prepared in the step (2) in 2-3h when the pressure in the reaction kettle is reduced by 0.25MPa, and stripping the reaction kettle to recover unreacted chloroethylene in the system when the pressure in the reaction kettle is reduced to be below 0.3 MPa;
(4) And (3) pouring out the materials in the reaction kettle, sequentially performing dehydration, rinsing, centrifugation and drying treatment, and then screening the dried materials by using a 40-mesh screen to obtain the material.
Example 1
The processing modification auxiliary agent comprises the following components in parts by weight:
example 2
The processing modification auxiliary agent comprises the following components in parts by weight:
example 3
The processing modification auxiliary agent comprises the following components in parts by weight:
example 4
The processing modification auxiliary agent comprises the following components in parts by weight:
example 5
The processing modification auxiliary agent comprises the following components in parts by weight:
comparative example 1 the same as example 1 except that butyl acrylate was used in place of vinyl versatate in comparative example 1.
Comparative example 2 the same as example 1, except that the dispersant used in comparative example 2 was a mixture of polyvinyl alcohol KH-20, hydroxypropylmethylcellulose E50, polyvinyl alcohol LL-02 in a weight ratio of 1.
Comparative example 3 the same as example 1, except that the dispersant used in comparative example 3 was a mixture of polyvinyl alcohol KH-20, hydroxypropylmethylcellulose E50, polyvinyl alcohol LL-02 in a weight ratio of 3.
The application comprises the following steps:
respectively adding the processing modification aids prepared in the examples 1-5 and the comparative examples 1-3 into a CPVC material system, carrying out melt extrusion by a conical double-screw extruder, and processing into a sheet with the thickness of 2mm, wherein the feeding speed of the double-screw extruder is 25rpm; the rotating speed of the double-screw extruder is 35rpm; the double-screw extruder is controlled by zone temperature, the temperature of a first zone is 170-175 ℃, the temperature of a second zone is 190-195 ℃, the temperature of a third zone is 193-198 ℃, the temperature of a fourth zone is 190-195 ℃, the extrusion material is subjected to vacuum forming and water cooling at the temperature of below 18 ℃ and is drawn at the speed of 2-3m/min, and the CPVC material system comprises the following components in parts by weight:
and (3) performance testing:
the CPVC thick sheets respectively processed and formed by the examples 1-5 and the comparative examples 1-3 are tested for relevant performances according to GB/T5135.19-2010, and the specific test results are shown in a table 1:
TABLE 1
| Test item | Vicat softening point/. Degree C | Notched impact strength/kJ · m -2 | Machining torque/N.m |
| Example 1 | 112.4 | 46.3 | 26.3 |
| Example 2 | 111.6 | 46.1 | 27.2 |
| Example 3 | 108.5 | 45.4 | 27.6 |
| Example 4 | 113.8 | 46.9 | 25.4 |
| Example 5 | 113.2 | 47.2 | 25.7 |
| Comparative example 1 | 107.2 | 44.1 | 29.6 |
| Comparative example 2 | 105.6 | 43.5 | 30.3 |
| Comparative example 3 | 102.4 | 42.3 | 29.3 |
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (2)
1. The processing modification auxiliary agent is characterized by comprising the following components in parts by weight:
49-59.5 parts of vinyl chloride
7-10.5 parts of vinylidene chloride
Ethylene versatate 3.5-10.5 parts
0.2 to 0.6 portion of initiator
2-5 parts of dispersant
100-130 parts of deionized water;
the sum of the parts by weight of the chloroethylene, the vinylidene chloride and the vinyl versatate is 70 parts;
the processing modified additive is prepared by the following steps in parts by weight:
(1) Adding vinyl versatate, an initiator, 3/4 deionized water and 3/4 parts of a dispersing agent into a reaction kettle in sequence according to the formula amount, vacuumizing, adding 1/2-3/5 parts of vinyl chloride into the reaction kettle when the vacuum degree reaches 0.09MPa, and stirring for 1-1.5 hours to uniformly disperse the materials;
(2) Adding the rest deionized water, the dispersing agent, vinyl chloride and vinylidene chloride into a stirring dispersion kettle, and stirring for 1-2h to obtain a fully dispersed monomer dispersion liquid;
(3) Heating the reaction kettle in the step (1) to 58-68 ℃, starting a reaction in the reaction kettle, continuously and uniformly adding the monomer dispersion liquid prepared in the step (2) within 2-3h when the pressure in the reaction kettle is reduced by 0.25MPa, and stripping the reaction kettle to recover unreacted chloroethylene in the system when the pressure in the reaction kettle is reduced to be below 0.3 MPa;
(4) Pouring out the materials in the reaction kettle, sequentially performing dehydration, rinsing, centrifugation and drying treatment, and then screening the dried materials by using a 40-mesh screen to obtain the material;
the dispersing agent is a mixture consisting of polyvinyl alcohol KH-20, hydroxypropyl methyl cellulose E50 and polyvinyl alcohol LL-02 in a weight ratio of 3.
2. A process modifying additive according to claim 1 wherein: the initiator is a mixture of azobisisobutyronitrile and tert-butyl peroxypivalate according to a weight ratio of 3.
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| CN202110947357.0A CN113717309B (en) | 2021-08-18 | 2021-08-18 | Processing modified additive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115181204B (en) * | 2022-07-05 | 2023-08-29 | 无锡洪汇新材料科技股份有限公司 | Chlorinated vinyl polymer and preparation method thereof |
| TWI828354B (en) | 2022-10-07 | 2024-01-01 | 南亞塑膠工業股份有限公司 | Pvc resin composition and method for manufacturing pipe having high heat resistance and transparency |
| CN116731224B (en) * | 2023-08-14 | 2023-10-27 | 山东亚大新材料有限公司 | Preparation method of chlorinated polyvinyl chloride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1347287A (en) * | 1970-06-02 | 1974-02-27 | Rohm & Haas | Modified vinyl halide polymer compositions |
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| JP5729286B2 (en) * | 2010-12-24 | 2015-06-03 | 日信化学工業株式会社 | Vinyl chloride resin, method for producing the same, and ink |
| CN105175604A (en) * | 2015-10-27 | 2015-12-23 | 无锡洪汇新材料科技股份有限公司 | Chloroethylene-vinylidene chloride-2-ethylhexyl acrylate-organotin copolymer emulsion and preparation method thereof |
| CN112521542A (en) * | 2020-11-18 | 2021-03-19 | 李丹丹 | Antibacterial emulsion for PVC and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1347287A (en) * | 1970-06-02 | 1974-02-27 | Rohm & Haas | Modified vinyl halide polymer compositions |
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